CN100428979C - Ammonia desulfurizing process and apparatus with crystallization inside tower - Google Patents
Ammonia desulfurizing process and apparatus with crystallization inside tower Download PDFInfo
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- CN100428979C CN100428979C CNB2005100408011A CN200510040801A CN100428979C CN 100428979 C CN100428979 C CN 100428979C CN B2005100408011 A CNB2005100408011 A CN B2005100408011A CN 200510040801 A CN200510040801 A CN 200510040801A CN 100428979 C CN100428979 C CN 100428979C
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- absorber portion
- circulating slot
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- main absorber
- gas
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 26
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002425 crystallisation Methods 0.000 title claims description 16
- 230000008025 crystallization Effects 0.000 title claims description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 6
- 239000006096 absorbing agent Substances 0.000 claims description 60
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 230000003647 oxidation Effects 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 239000007921 spray Substances 0.000 claims description 21
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 12
- 238000006477 desulfuration reaction Methods 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000003517 fume Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 238000012423 maintenance Methods 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000002362 anti-crystal effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The present invention belongs to the field of environment protection apparatus, and is especially crystallizing ammonia type desulfurizing process and apparatus for removing and recovering SO2 from fume. The apparatus includes one desulfurizing tower, one absorbing and circulating tank outside the tower, one concentrating and circulating tank, one ammonium sulfate thickener, one centrifuger and one drier. It features the crystallizing section and oxidizing section set below the fume inlet inside the desulfurizing tower, the connection of the crystallizing section with the concentrating and circulating tank, the connection of the oxidizing section outlet with the absorbing and circulating tank, and the successive connection of the other parts. The present invention has low cost and convenient apparatus maintenance and operation.
Description
Technical field
The invention belongs to the environmental protection equipment technical field, relate to a kind of crystallization inside tower ammonia desulfurizing process and device that sulfur in smoke is removed and recycles of being used for.
Background technology
Traditional flue gas desulfurization technique mainly adopts calcium method desulfur technology, and what there is secondary pollution and desulfurated plaster is difficult to defectives such as disposal.Compare with calcium method sulfur removal technology, existing ammonia desulfurizing process is to utilize ammonia to absorb sulfur in smoke, and its reaction is solution-air or gas-gas-phase reaction, and reaction speed is fast, absorbent utilization rate height, and the absorption equipment volume can reduce greatly.But problems the such as when ammonia process of desulfurization was applied to the desulfurization of fire coal boiler fume, existing all kinds of technology ubiquities that ammonia consumption is high, aerosol is difficult to elimination, absorption liquid processing cost height, operation easier are big.Because ammonia type flue gas desulfurizing is to absorb sulfur dioxide with ammonia to generate ammonium sulfite usually, use air oxidation then, but the ammonium sulfite of high concentration can not quick and completely be direct oxidation into ammonium sulfate, but under low concentration, obtain product by evaporating and concentrating process after the oxidation, its evaporation capacity is big, the big and long flow path of energy consumption, and equipment is many, occupation of land is big, the operating cost height, the economy of device is relatively poor.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of and make absorbent with ammonia, can integrate the washing, cooling, absorption, dehydration, demist of flue gas and absorb after byproduct oxidation, concentrate, the crystallization inside tower ammonia desulfurizing process and the device of function such as crystallization, make it under the condition that guarantees desulfuration efficiency and byproduct quality, can reduce equipment for after-treatment and energy consumption in fact, reduce operating cost.
Crystallization inside tower ammonia desulfuration equipment of the present invention includes a desulfurizing tower and is positioned at the outer absorption circulating slot of tower, concentrated circulating slot, sulphur ammonium stiff device, centrifuge and drier; The middle part of desulfurizing tower is provided with into mouth, and the top sets out mouth, is advancing to be provided with from the bottom to top between mouth and the outlet flue cooling absorber portion, main absorber portion, dehydrating demisting section; Be provided with the gas cap that only passes through for flue gas between cooling absorber portion and the main absorber portion, the cooling absorber portion is provided with the several layers spray equipment, and main absorber portion is provided with several layers filler and spray equipment, and the dehydrating demisting section is provided with demist filler and fresh water (FW) spray equipment; Advancing below the mouth, be provided with crystallized region and oxidation panel from top to bottom, separating mutually by dividing plate between crystallized region and the oxidation panel; Crystallized region top is provided with the solution overfall, and the solution overfall passes to concentrated circulating slot; The oxidation panel bottom is provided with the air sparger that communicates with compressed air, and the oxidation panel bottom is provided with the absorption liquid inlet, and oxidation panel top is provided with the absorption liquid outlet, and the absorption liquid inlet is connected with the outlet of main absorber portion bottom, and the absorption liquid outlet feeds and absorbs circulating slot; The export pipeline that absorbs circulating slot is divided into three the tunnel, and the first via passes to the cooling absorber portion, and the second the tunnel passes to the spray equipment of main absorber portion lower floor, and Third Road passes to the spray equipment on main absorber portion upper strata; The overfall that absorbs circulation section passes to concentrated circulating slot, and the export pipeline that concentrates circulating slot is divided into two-way, and one the tunnel feeds sulphur ammonium stiff device, and another road passes to the spray equipment of cooling absorber portion; The magma outlet of sulphur ammonium stiff device is connected to centrifuge and drier, and the mother liquor overfall of sulphur ammonium stiff device passes to concentrated circulating slot; In addition, the spray equipment of main absorber portion and concentrate circulating slot and is connected with the storage tank of ammonia absorbent respectively is used for benefit and goes into the ammonia absorbent.Crystallized region can be provided with agitating device, and this agitating device can adopt gas stirring device, and its air inlet is connected with the gas outlet of oxidation panel.
Crystallization inside tower ammonia desulfurizing process flow process of the present invention is as follows:
A. flue gas enters desulfurizing tower from the mouth that advances at desulfurizing tower middle part, lower the temperature by absorption liquid spray and preliminary the absorption carried out desulphurization reaction after gas distributor enters main absorber portion at the cooling absorber portion, entering the dehydrating demisting section then carries out discharging behind the dehydrating demisting, the liquid-gas ratio of cooling absorber portion was controlled at 1: 2000～1: 200, the liquid-gas ratio of main absorber portion was controlled at 1: 5000～1: 200, main absorber portion amounts of ammonium salt≤35%;
B. the absorption liquid that main absorber portion gets off enters oxidation panel by annotating absorber portion, carries out oxidation by the air that pumps into, and the oxidation time of staying is not less than 1 hour, and the concentration of ammonium sulfate solution is not more than 35%, enters the absorption circulating slot by oxidation panel then;
C. be divided into three the tunnel by absorbing the absorption liquid that circulating slot pumps, the first via is as the intermediate products absorber portion that advances to lower the temperature, and it accounts for the 5-15% of output quantity; The second the tunnel advances main absorber portion epimere, and it accounts for the 35-50% of output quantity; Third Road advances main absorber portion hypomere, and it accounts for the 35-60% of output quantity, and mends the ammonia absorbent before advancing tower;
D. the absorption liquid that is overflowed by absorption circulating slot overfall enters concentrated circulating slot; Be divided into two-way by the concentrate that concentrates circulating slot output, the first via is sent post processing stiff device stiff, and it accounts for the 15-30% of output quantity; Another road (about 70-85%) enters Ta Nei from the cooling absorber portion of desulfurizing tower and contacts with flue gas adverse current, in the crystallized region crystallization, overflows to then and concentrates circulating slot and recycle behind the evaporation transpiring moisture of high-temperature flue gas;
E. at crystallized region, solution should be greater than 30 minutes, to form a brilliant ammonia sulfate crystal greater than 0.2mm at dwell time in the tower; For anti-crystal sedimentation, can be provided with agitating device at crystallized region, agitating device can adopt air agitating device or electric mixing device etc., and the air agitating device can adopt the gas of oxidation panel discharge as gas source;
F. the slurries that enter the stiff device by concentrated circulating slot separate in the stiff device, mother liquor returns concentrated circulating slot, solid content is sent from the scheming separation greater than 35% magma, and the centrifuge mother liquor returns concentrated circulating slot, and water content send drier further to be dried to finished product less than 1% sulphur ammonium.
The present invention is by the Multiple Cycle of absorption liquid, can in desulfurizing tower, realize the crystallization of byproduct of ammonium sulfate, need not to carry out condensing crystallizing, thereby guaranteeing under the normal desulfurization efficiency prerequisite, not only saved investment but also greatly reduced operating cost at a large amount of steam of postprocessing working procedures consumption.
Description of drawings
Fig. 1 is the apparatus structure and the process flow diagram of the embodiment of the invention.
Among the figure: 1 for desulfurizing tower, 11 for advance mouth, 12 for outlet flue, 13 for cooling absorber portion, 14 be primarily absorption section, 15 for the dehydrating demisting section, 16 for gas cap, 17 for spray equipment, 18 for crystallized region, 19 for oxidation panel, 181 for the solution overfall, 182 for agitating device, 191 for absorption liquid inlet, 192 for the absorption liquid outlet, 193 for air sparger, 2 for absorb circulating slot, 3 for concentrate circulating slot, 4 for sulphur ammonium stiff device, 5 be that centrifuge, 6 is a drier.
The specific embodiment
Embodiment:
Handle object and be one of the coal-burning boiler of evaporation capacity 220t/h, exhaust gas volumn 280000Nm
3/ h, boiler coal consumption 32t/h, coal-fired full sulphur 3%, 140 ℃ of exhaust gas temperatures.
Desulfurization process and the device as Fig. 1,39 meters of nucleus equipment desulfurization tower heights, 7.8 meters of diameters, main absorber portion filler is the Y125 ripple packing.The mouth top advanced of tower is the cooling absorber portion, and cooling absorber portion upper strata (apart from the positions of cooling absorber portion with 1.5 meters of main absorber portion space bars) are the additional liquid spraying layer of one deck lower concentration absorbing liquid (set up defences blocking sprayer 9); Cooling absorber portion lower floor (apart from the positions of cooling absorber portion with 3.5 meters of main absorber portion space bars) is one deck concentrate spraying layer (sets up defences blocking sprayer 23); Establish the crystallization inside tower layer between the crystallized region bottom baffles at the bottom of the smoke inlet, the crystallized region overfall is apart from 1 meter on dividing plate, and as gas stirring device, this device draws the oxidation panel oxidation air and mixes gas at the uniform air-distribution pipe of crystallized region.
Stiff device φ 4500 * 3500, the disposal ability of centrifuge, drier is 5t/h, the thermal source of drier is a steam.
Operating parameter:
Absorber portion---absorb circulation fluid ammonium salt-containing concentration 32%, spray flux 300m
3/ h replenishes liquefied ammonia 780.3kg/h, 53 ℃ of the flue-gas temperatures of smoke absorption section.
The cooling absorber portion---concentrating circulation fluid concentration is solid content 10%, spray flux 160m
3/ h, flue gas go out the to lower the temperature temperature of absorber portion is 66 ℃.
Dehydrating demisting section---rate of water make-up 12m
3/ h.
Result:
Content of sulfur dioxide 174.8mg/Nm in the tail gas
3, the content 3mg/Nm of ammonia in the tail gas
3Desulfurizer total pressure drop 970Pa.By-product meets the ammonium sulfate 3366kg/h of GB535 standard primes, and steam consumption (drier vapour) is 100kg/h, and power consumption is 430kw.
Claims (5)
1, a kind of crystallization inside tower ammonia desulfuration equipment is characterized in that: it includes a desulfurizing tower and is positioned at the outer absorption circulating slot of tower, concentrated circulating slot, sulphur ammonium stiff device, centrifuge and drier; The middle part of desulfurizing tower is provided with into mouth, and the top sets out mouth, is advancing to be provided with from the bottom to top between mouth and the outlet flue cooling absorber portion, main absorber portion, dehydrating demisting section; Be provided with the gas cap that only passes through for flue gas between cooling absorber portion and the main absorber portion, the cooling absorber portion is provided with the several layers spray equipment, and main absorber portion is provided with several layers filler and spray equipment, and the dehydrating demisting section is provided with demist filler and fresh water (FW) spray equipment; Advancing below the mouth, be provided with crystallized region and oxidation panel from top to bottom, separating mutually by dividing plate between crystallized region and the oxidation panel; Crystallized region top is provided with the solution overfall, and the solution overfall passes to concentrated circulating slot; The oxidation panel bottom is provided with the air sparger that communicates with compressed air, and the oxidation panel bottom is provided with the absorption liquid inlet, and oxidation panel top is provided with the absorption liquid outlet, and the absorption liquid inlet is connected with the outlet of main absorber portion bottom, and the absorption liquid outlet feeds and absorbs circulating slot; The export pipeline that absorbs circulating slot is divided into three the tunnel, and the first via passes to the cooling absorber portion, and the second the tunnel passes to the spray equipment on main absorber portion upper strata, and Third Road passes to the spray equipment of main absorber portion lower floor; The overfall that absorbs circulating slot passes to concentrated circulating slot, and the export pipeline that concentrates circulating slot is divided into two-way, and one the tunnel feeds sulphur ammonium stiff device, and another road passes to the spray equipment of cooling absorber portion; The magma outlet of sulphur ammonium stiff device is connected to centrifuge and drier, and the mother liquor overfall of sulphur ammonium stiff device passes to concentrated circulating slot; In addition, the spray equipment of main absorber portion and concentrated circulating slot are connected with the storage tank of ammonia absorbent respectively.
2, crystallization inside tower ammonia desulfuration equipment according to claim 1, it is characterized in that: crystallized region is provided with agitating device.
3, crystallization inside tower ammonia desulfuration equipment according to claim 2 is characterized in that: described agitating device is a gas distribution tube, and its air inlet is connected with the gas outlet of oxidation panel.
4, a kind of crystallization inside tower ammonia desulfurizing process that carries out in the described desulfurizer of claim 1 is characterized in that:
A. flue gas enters desulfurizing tower from the mouth that advances at desulfurizing tower middle part, lower the temperature by absorption liquid spray and preliminary the absorption carried out desulphurization reaction after gas cap enters main absorber portion at the cooling absorber portion, entering the dehydrating demisting section then carries out discharging behind the dehydrating demisting, the liquid-gas ratio of cooling absorber portion is controlled at 1: 2000-1: 200, the liquid-gas ratio of main absorber portion is controlled at 1: 5000-1: 200, and main absorber portion amounts of ammonium salt≤35%;
B. the absorption liquid that main absorber portion gets off enters oxidation panel by main absorber portion, carries out oxidation by the air that pumps into, and the oxidation time of staying is not less than 1 hour, and the concentration of ammonium sulfate solution is not more than 35%, enters the absorption circulating slot by oxidation panel then;
C. the absorption liquid by absorption liquid circulating slot output is divided into three the tunnel, and the first via is as the intermediate products absorber portion that advances to lower the temperature, and it accounts for the 5-15% of output quantity; The second tunnel spray equipment that passes to main absorber portion upper strata advances main absorber portion epimere, and it accounts for the 35-50% of output quantity; The spray equipment that Third Road passes to main absorber portion lower floor advances main absorber portion hypomere, and it accounts for the 35-60% of output quantity, and mends the ammonia absorbent before advancing tower;
D. be divided into two-way by the concentrate that concentrates circulating slot output, the first via is sent sulphur ammonium stiff device stiff, and it accounts for the 15-30% of output quantity; Another road enters Ta Nei from the cooling absorber portion of desulfurizing tower and contacts with flue gas adverse current, in the crystallized region crystallization, overflows to then and concentrates circulating slot and recycle behind the evaporation transpiring moisture of high-temperature flue gas;
E. at crystallized region, solution at dwell time in the tower greater than 30 minutes;
F. the slurries that enter sulphur ammonium stiff device by concentrated circulating slot separate in sulphur ammonium stiff device, mother liquor returns concentrated circulating slot, solid content is sent from the scheming separation greater than 35% magma, and the centrifuge mother liquor returns concentrated circulating slot, and water content send drier further to be dried to finished product less than 1% sulphur ammonium.
5, according to the crystallization inside tower ammonia desulfurizing process of claim 4, it is characterized in that: be provided with agitating device at crystallized region, agitating device adopts the air agitating device, and the gas that the air agitating device is discharged with oxidation panel is as gas source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100408011A CN100428979C (en) | 2005-06-28 | 2005-06-28 | Ammonia desulfurizing process and apparatus with crystallization inside tower |
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|---|---|---|---|
| CNB2005100408011A CN100428979C (en) | 2005-06-28 | 2005-06-28 | Ammonia desulfurizing process and apparatus with crystallization inside tower |
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| CN1887409A CN1887409A (en) | 2007-01-03 |
| CN100428979C true CN100428979C (en) | 2008-10-29 |
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